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The greater Agulhas Current region is an important component of the climate system, yet its influence on carbon and nutrient cycling is poorly understood. Here, we use nitrate isotopes (δ15N, δ18O, Δ(15–18) = δ15N–δ18O) to trace regional water mass circulation and investigate nitrogen cycling in the Agulhas Current and adjacent recirculating waters. The deep and intermediate waters record processes occurring remotely, including partial nitrate assimilation in the Southern Ocean and denitrification in the Arabian Sea. In the thermocline and surface, tropically sourced waters are biogeochemically distinct from adjacent subtropically sourced waters, confirming inhibited lateral mixing across the current core. (Sub)tropical thermocline nitrate δ15N is lower (4.9–5.8‰) than the sub-thermocline source, Subantarctic Mode Water (6.9‰); we attribute this difference to local N2 fixation. Using a one-box model to simulate the newly fixed nitrate flux, we estimate a local N2 fixation rate of 7–25 Tg N.a−1, with the upper limit likely biased high. In the mixed layer, nitrate δ15N and δ18O rise in unison, indicating that phytoplankton nitrate assimilation dominates in surface waters, with nitrification restricted to deeper waters. Because nitrate assimilation and nitrification are vertically decoupled, the rate of nitrate assimilation plus N2 fixation can be used to approximate carbon export. Thermocline and mixed-layer nitrate Δ(15–18) is low, due to both N2 fixation and coupled partial nitrate assimilation and nitrification. Similarly low-Δ(15–18) nitrate in Agulhas rings indicates leakage of low-δ15N nitrogen into the South Atlantic, which should be recorded in the organic matter sinking to the seafloor, providing a potential tracer of past Agulhas leakage.

During glacial terminations, massive iceberg discharges and meltwater pulses in the North Atlantic triggered a shutdown of the Atlantic Meridional Overturning Circulation (AMOC). Speleothem calcium carbonate oxygen isotope records (δ18OCc) indicate that the collapse of the AMOC caused dramatic changes in the distribution and variability of the East Asian and Indian monsoon rainfall. However, the mechanisms linking changes in the intensity of the AMOC and Asian monsoon δ18OCc are not fully understood. Part of the challenge arises from the fact that speleothem δ18OCc depends on not only the δ18O of precipitation but also temperature and kinetic isotope effects. Here we quantitatively deconvolve these parameters affecting δ18OCc by applying three geochemical techniques in speleothems covering the penultimate glacial termination. Our data suggest that the weakening of the AMOC during meltwater pulse 2A caused substantial cooling in East Asia and a shortening of the summer monsoon season, whereas the collapse of the AMOC during meltwater pulse 2B (133,000 years ago) also caused a dramatic decrease in the intensity of the Indian summer monsoon. These results reveal that the different modes of the AMOC produced distinct impacts on the monsoon system., Nature Geoscience, 14 (12), ISSN:1752-0908, ISSN:1752-0894

The modern Pacific Ocean hosts the largest oxygen-deficient zones (ODZs), where oxygen concentrations are so low that nitrate is used to respire organic matter. The history of the ODZs may offer key insights into ocean deoxygenation under future global warming. In a 12-My record from the southeastern Pacific, we observe a >10‰ increase in foraminifera-bound nitrogen isotopes (15N/14N) since the late Miocene (8 to 9 Mya), indicating large ODZs expansion. Coinciding with this change, we find a major increase in the nutrient content of the ocean, reconstructed from phosphorus and iron measurements of hydrothermal sediments at the same site. Whereas global warming studies cast seawater oxygen concentrations as mainly dependent on climate and ocean circulation, our findings indicate that modern ODZs are underpinned by historically high concentrations of seawater phosphate., Proceedings of the National Academy of Sciences of the United States of America, 119 (45), ISSN:0027-8424, ISSN:1091-6490

During the last ice age, the Northern Hemisphere experienced a series of abrupt millennial-scale climatic changes linked to variations in the strength of the Atlantic Meridional Overturning Circulation and sea-ice extent. However, our understanding of their impacts on decadal-scale climate variability in central Europe has been limited by the lack of high-resolution continental archives. Here, we present a near annual-resolution climate proxy record of central European temperature reconstructed from the Eifel maar lakes of Holzmaar and Auel in Germany, spanning the past 60,000 years. The lake sediments reveal a series of previously undocumented multidecadal climate cycles of around 20 to 150 years that persisted through the last glacial cycle. The periodicity of these cycles suggests that they are related to the Atlantic multidecadal climate oscillations found in the instrumental record and in other climate archives during the Holocene. Our record shows that multidecadal variability in central Europe was strong during all warm interstadials, but was substantially muted during all cold stadial periods. We suggest that this decrease in multidecadal variability was the result of the atmospheric circulation changes associated with the weakening of the Atlantic Meridional Overturning Circulation and the expansion of North Atlantic sea-ice cover during the coldest parts of the last ice age. Central European multidecadal climate variability was subdued during cold stadials through the last glacial cycle due to atmospheric and oceanic circulation shifts, according to almost annual-resolution terrestrial climate proxy records from varved maar lakes in Germany.

Salinity-driven density stratification of the upper Arctic Ocean isolates sea-ice cover and cold, nutrient-poor surface waters from underlying warmer, nutrient-rich waters. Recently, stratification has strengthened in the western Arctic but has weakened in the eastern Arctic; it is unknown if these trends will continue. Here we present foraminifera-bound nitrogen isotopes from Arctic Ocean sediments since 35,000 years ago to reconstruct past changes in nutrient sources and the degree of nutrient consumption in surface waters, the latter reflecting stratification. During the last ice age and early deglaciation, the Arctic was dominated by Atlantic-sourced nitrate and incomplete nitrate consumption, indicating weaker stratification. Starting at 11,000 years ago in the western Arctic, there is a clear isotopic signal of Pacific-sourced nitrate and complete nitrate consumption associated with the flooding of the Bering Strait. These changes reveal that the strong stratification of the western Arctic relies on low-salinity inflow through the Bering Strait. In the central Arctic, nitrate consumption was complete during the early Holocene, then declined after 5,000 years ago as summer insolation decreased. This sequence suggests that precipitation and riverine freshwater fluxes control the stratification of the central Arctic Ocean. Based on these findings, ongoing warming will cause strong stratification to expand into the central Arctic, slowing the nutrient supply to surface waters and thus limiting future phytoplankton productivity., Nature Geoscience, 14 (9), ISSN:1752-0908, ISSN:1752-0894

For times prior to those represented by the air trapped in Antarctic ice core records, the concentration of CO2 in the atmosphere must be reconstructed using geochemical proxies. The δ13C of particulate organic carbon (POC) produced in ocean surface waters has previously been observed to covary with the concentration of CO2 in the water. Relative to bulk sedimentary organic carbon, the minute quantity of organic matter trapped within the shell walls of planktonic foraminifera, “foraminifera-bound organic matter” (FBOM), has the potential advantage of being protected from diagenetic alteration and contamination by allochthonous organic matter. Here, with new protocols and instrumentation, FBOM-δ13C is investigated as a potential proxy for the aqueous CO2 concentration ([CO2(aq)]) and thus the partial pressure of CO2 (pCO2) in past surface waters. We achieve a full method precision for FBOM-δ13C of 0.4‰ (1SD) on sample sizes of 20 nanomole C by adding a cryofocus step, a helium sheath flow to the oxidation and reduction reactors, and other modifications to an elemental analyzer and by introducing new approaches to reduce contamination during sample preparation. FBOM-δ13C was analyzed in core-top sediments from the eastern tropical Pacific that span the equatorial maximum in surface water [CO2(aq)]. FBOM-δ13C is lower than predicted for marine phytoplankton, consistent with a substantial lipid component in FBOM. Anticorrelation is observed between FBOM-δ13C and climatological [CO2(aq)]; the relationship is statistically significant (P

Dissolved oxygen (O2) is essential for most ocean ecosystems, fuelling organisms’ respiration and facilitating the cycling of carbon and nutrients. Oxygen measurements have been interpreted to indicate that the ocean’s oxygen-deficient zones (ODZs) are expanding under global warming. However, models provide an unclear picture of future ODZ change in both the near term and the long term. The paleoclimate record can help explore the possible range of ODZ changes in warmer-than-modern periods. Here we use foraminifera-bound nitrogen (N) isotopes to show that water-column denitrification in the eastern tropical North Pacific was greatly reduced during the Middle Miocene Climatic Optimum (MMCO) and the Early Eocene Climatic Optimum (EECO). Because denitrification is restricted to oxygen-poor waters, our results indicate that, in these two Cenozoic periods of sustained warmth, ODZs were contracted, not expanded. ODZ contraction may have arisen from a decrease in upwelling-fuelled biological productivity in the tropical Pacific, which would have reduced oxygen demand in the subsurface. Alternatively, invigoration of deep-water ventilation by the Southern Ocean may have weakened the ocean’s ‘biological carbon pump’, which would have increased deep-ocean oxygen. The mechanism at play would have determined whether the ODZ contractions occurred in step with the warming or took centuries or millennia to develop. Thus, although our results from the Cenozoic do not necessarily apply to the near-term future, they might imply that global warming may eventually cause ODZ contraction., Nature, 609 (7925), ISSN:0028-0836, ISSN:1476-4687

Trophic position is a fundamental characteristic of animals, yet it is unknown in many extinct species. In this study, we ground-truth the 15N/14N ratio of enameloid-bound organic matter (δ15NEB) as a trophic level proxy by comparison to dentin collagen δ15N and apply this method to the fossil record to reconstruct the trophic level of the megatooth sharks (genus Otodus). These sharks evolved in the Cenozoic, culminating in Otodus megalodon, a shark with a maximum body size of more than 15 m, which went extinct 3.5 million years ago. Very high δ15NEB values (22.9 ± 4.4‰) of O. megalodon from the Miocene and Pliocene show that it occupied a higher trophic level than is known for any marine species, extinct or extant. δ15NEB also indicates a dietary shift in sharks of the megatooth lineage as they evolved toward the gigantic O. megalodon, with the highest trophic level apparently reached earlier than peak size., Science Advances, 8 (25), ISSN:2375-2548

Summary of Ilse Seibold's vita Ilse Seibold, née Usbeck, was born May 8, 1925 in Breslau, Silesia, and went to school in Halle/Saale during WW2. She started her studies of geology and paleontology at the University of Halle and at the Humboldt University in Berlin, and later at the University of Tübingen, where she received her doctorate as micropaleontologist in 1951 with Otto Schindewolf as her supervisor. She remained active as productive scientist over many decades. In 1952, she married Dr. Eugen Seibold, who in 1958 became professor at Kiel University, founded one of Europe's most important institutes for marine geology, and later became president of the German Science Foundation (DFG), and subsequently of the European Science Foundation (ESF). Being a scientist herself Ilse Seibold soon evolved to a deeply reflective insider of geological sciences. She followed her husband during his scientific career from his appointments in Tübingen, Bonn, Karlsruhe, Kiel, to Bonn and Strasbourg/Freiburg i.Br. She accompanied Eugen on his sabbatical leave at Scripps Institution of Oceanography in La Jolla, CA. She participated in countless international scientific meetings. Together with Eugen she published many papers that document her independence and autonomy as scientist. She gained deep insights into the origins of the geosciences and their historical evolution, up to the ideas of fine arts. We are happy that she documented in her publications a broad range of her scientific and distinguished-humane impressions.

Historical coral skeleton (CS) δ18 O and δ15 N records were produced from samples recovered from sedimentary deposits, held in natural history museum collections, and cored into modern coral heads. These records were used to assess the influence of global warming and regional eutrophication, respectively, on the decline of coastal coral communities following the development of the Pearl River Delta (PRD) megacity, China. We find that, until 2007, ocean warming was not a major threat to coral communities in the Pearl River estuary; instead, nitrogen (N) inputs dominated impacts. The high but stable CS-δ15 N values (9‰-12‰ vs. air) observed from the mid-Holocene until 1980 indicate that soil and stream denitrification reduced and modulated the hydrologic inputs of N, blunting the rise in coastal N sources during the early phase of the Pearl River estuary urbanization. However, an unprecedented CS-δ15 N peak was observed from 1987 to 1993 (>13‰ vs. air), concomitant to an increase of NH4+ concentration, consistent with the rapid Pearl River estuary urbanization as the main cause for this eutrophication event. We suggest that widespread discharge of domestic sewage entered directly into the estuary, preventing removal by natural denitrification hotspots. We argue that this event caused the dramatic decline of the Pearl River estuary coral communities reported from 1980 to 2000. Subsequently, the coral record shows that the implementation of improved wastewater management policies succeeded in bringing down both CS-δ15 N and NH4+ concentrations in the early 2000s. This study points to the potential importance of eutrophication over ocean warming in coral decline along urbanized coastlines and in particular in the vicinity of megacities.

We reconstructed changes in summer and winter precipitation using a well-dated (±18 years 2σ error) speleothem spanning 4.2-3.1 ka BP from Dharamjali Cave in the central Himalaya. The record was sampled at a sub-annual resolution for a suite of trace elements, as well oxygen and carbon stable isotopes. Calcium isotopes at decadal resolution provide additional hydroclimatic evidence. This DHAR-1 stalagmite records a 230-year period of increased drought frequency in both the summer and winter seasons after 4.2 ka BP, with aridity events centered on 4.19, 4.11 and 4.02 ka BP each lasting between 25 and 90 years. The data after 3.97 ka BP support a recovery in summer monsoon rainfall, peaking around 3.7 ka BP. The significance of this new record includes remarkable coherence between the moisture proxies over 4.2-3.97 ka BP in a well-dated record, which provides confidence in the duration of droughts and timing of monsoon recovery. It also places seasonal climate variability on a timescale relevant to human decision-making, which is particularly significant for this region nearby the Indus River Basin. The Indus Civilization reached its urban apex by 4.2 ka BP, and archaeologists have documented a shift in settlement locations, population, health, and agricultural strategies thereafter for a period of several centuries. This stalagmite record provides valuable insights into seasonal precipitation availability during a critical climatic and cultural transition phase., EGUsphere

Nitrogen isotoperatios (δ15N) are a well-established tool for investigating the dietary and trophic behavior of animals in terrestrial and marine food webs. To date, δ15N values in fossils have primarily been measured in collagen extracted from bone or dentin, which is susceptible to degradation and rarely preserved in deep time (>100,000 years). In contrast,tooth enamelorganic matter is protected from diagenetic alteration by the mineral structure of hydroxyapatite and thus is often preserved overgeological time. However, due to the low nitrogen content (isotopic compositionhas been prevented by the analytical limitations of traditional methods. Here, we present a novel application of the oxidation-denitrification method that allows measurement of δ15N values in tooth enamel (δ15Nenamel). This method involves the oxidation of nitrogen in enamel-bound organic matter to nitrate followed by bacterial conversion of nitrate to N2O, and requires ≥100 times less nitrogen than traditional approaches. To demonstrate that δ15Nenamelvalues record diet and trophic behavior, we conducted a controlled feeding experiment with rats and guinea pigs (n=37). We determined that nitrogen concentration in tooth enamel (x̄=5.0±1.0 nmol/mg) is sufficient for δ15Nenamelanalyses with ≥5 mg untreated enamel powder. The nitrogen isotope composition of enamel reflects diet with an enrichment (Δ15Nenamel-diet) of ca. 2–4‰. δ15Nenamelvalues differ significantly between dietary groups and clearly record a shift from pre-experimental to experimental diet. The small sample size required (≤5 mg) by this method permits analyses of sample size-limited, diagenetically robust tooth enamel, and, as such it represents a promising new dietary proxy for reconstructing food webs and investigating thetrophic ecologyof extant and extinct taxa.

Ocean circulation supplies the surface ocean with the nutrients that fuel global ocean productivity. However, the mechanisms and rates of water and nutrient transport from the deep ocean to the upper ocean are poorly known. Here, we use the nitrogen isotopic composition of nitrate to place observational constraints on nutrient transport from the Southern Ocean surface into the global pycnocline (roughly the upper 1.2 km), as opposed to directly from the deep ocean. We estimate that 62 ± 5% of the pycnocline nitrate and phosphate originate from the Southern Ocean. Mixing, as opposed to advection, accounts for most of the gross nutrient input to the pycnocline. However, in net, mixing carries nutrients away from the pycnocline. Despite the quantitative dominance of mixing in the gross nutrient transport, the nutrient richness of the pycnocline relies on the large-scale advective flow, through which nutrient-rich water is converted to nutrient-poor surface water that eventually flows to the North Atlantic., info:eu-repo/semantics/published

Deepwater circulation significantly changed during the last deglaciation from a shallow to a deep-reaching overturning cell. This change went along with a drawdown of isotopically light waters into the abyss and a deep ocean warming that changed deep ocean stratification from a salinity-to a temperature-controlled mode. Yet, the exact mechanisms causing these changes are still unknown. Furthermore, the long-standing idea of a complete shutdown of North Atlantic deepwater formation during Heinrich Stadial 1 (HS1) (17.5–14.6 kyr BP) remains prevalent. Here, we present a new compilation of benthic δ13C and δ18O data from the North Atlantic at high temporal resolution with consistent age models, established as part of the international PAGES working group OC3, to investigate deepwater properties in the North Atlantic. The extensive compilation, which includes 105 sediment cores, reveals different water masses during HS1. A water mass with heavy δ13C and δ18O signature occupies the Iceland Basin, whereas between 20 and 50°N, a distinct tongue of 18O depleted, 13C enriched water reaches down to 4000 m water depths. The heavy δ13C signature indicates active deepwater formation in the North Atlantic during HS1. Differences in its δ18O signature indicate either different sources or an alteration of the deepwater on its southward pathway. Based on these results, we discuss concepts of deepwater formation in the North Atlantic that help to explain the deglacial change from a salinity-driven to a temperature-driven circulation mode. Highlights • Spatial analyses of benthic δ13C and δ18O data from OC3 Atlantic compilation for HS1. • Heavy δ13C, light δ18O waters migrated into deep western North Atlantic basin during HS1. • Active deepwater formation between 30 and 60°N in the North Atlantic during HS1. • New concepts for transport of isotopically light δ18O into deep ocean. • Major contribution of North Atlantic waters to deglacial deep ocean stratification changes.

Understanding oceanic cadmium (Cd) cycling is paramount due to its micronutrient‐like behavior in seawater, which has been inferred from its similarity to phosphate (PO4) cycling. Cadmium concentrations follow a nutrient‐like consumption‐regeneration cycle in the top of the water column and are mainly controlled by water mass mixing and circulation in the deep ocean. However, an additional scavenging mechanism through cadmium sulfide (CdS) precipitates, occurring within sinking biogenic particles in oxygen deficient zones (ODZ), has been proposed. In this study, we report Cd stable isotope and concentration data for seven vertical seawater profiles sampled during GEOTRACES cruise GA08 in the northern Cape and Angola Basins, which feature a significant ODZ along their eastern margins. Outside the ODZ, Cd cycling is similar to that previously reported for the South Atlantic. While water mass mixing largely controls deep ocean Cd isotope signatures, Cd isotope fractionation in surface waters can be modelled as an open system at steady‐state buffered by organic ligand complexation. In the ODZ, stronger Cd depletion relative to PO4 is associated with a shift in δ114Cd towards heavier values, which is indicative of CdS precipitation. Our interpretation is supported by experimental CdS precipitation data and a size‐resolved particle model involving bacterial sulfate reduction as a precursor of CdS. Our estimates of the CdS flux to the seafloor (107 to 109 mol yr‐1) indicate that CdS precipitation is a significant process of Cd removal and constitutes a non‐negligible Cd sink that needs to be better quantified by Cd isotope analyses of marine sediments.

The Indonesian Throughflow (ITF) controls the oceanic flux of heat and salt between the Pacific and Indian Oceans and therewith plays an important role in modulating the meridional overturning circulation and low latitude hydrological cycle. Here, we report new sea surface temperature and aridity records from the west coast of Australia (IODP Site U1460), which allow us to assess the sensitivity of the eastern Indian Ocean to the major reorganization of Earth’s climate that occurred during the Mid-Pleistocene Transition. Our records indicate glacial coolings at 1.55 and 0.65 million years ago that are best explained by a weakening of the ITF as a consequence of global sea level and tectonic changes. These coincide with the development of pronounced gradients in the carbon isotope composition of the different ocean basins and with substantial changes in regional aridity, suggesting that the restrictions of the ITF influenced both the evolution of global ocean circulation and the development of the modern hydrological cycle in Western Australia., Scientific Reports, 9 (1), ISSN:2045-2322

Circulation more than temperature Changes in continental configuration and sea level affected the ocean's oxygen levels and the rate of denitrification between 70 and 30 million years ago. That finding by Kast et al. shows a fundamental difference from the modern ocean, in which the extent of suboxia is controlled primarily by global temperature. Changes in the nitrogen isotopic composition of marine organic matter correlate with the collision of India and Asia and the circulation changes that occurred as a result. Later, isotopic composition changed further in response to a fall in sea level as global cooling caused ice sheets to grow. Science , this issue p. 386

Both the nitrogen (N) isotopic composition (d15N) of the nitrate source and the magnitude of isotope discrimination associated with nitrate assimilation are required to estimate the degree of past nitrate consumption from the d15N of organic matter in Southern Ocean sediments (e.g. preserved within diatom microfossils). It has been suggested that the amplitude of isotope discrimination (i.e. the isotope effect) correlates with mixed layer depth, driven by a physiological response of phytoplankton to light availability, which introduces complexity to the interpretation of sedimentary records. However, most of the isotope effect estimates that underpin this hypothesis derive from acid-preserved water samples, from which nitrite would have been volatilized and lost during storage. Nitrite d15N in Antarctic Zone surface waters is extremely low (61 ± 20‰), consistent with the expression of an equilibrium isotope effect associated with nitrate–nitrite interconversion. Its loss from the combinednitrate + nitrite pool would act to raise the d15N of nitrate, potentially yielding overestimation of the isotope effect. Here, we revisit the nitrate assimilation isotope effect in the Antarctic Zone with measurements of the d15N and concentration of nitrate with and without nitrite, using frozen sea water samples from 5 different cruises that collectively cover all sectors of the Southern Ocean. The N isotope effect estimated using nitrate + nitrite d15N is relatively constant (5.5 ± 0.6‰) across the Antarctic Zone, shows no relationship with mixed layer depth, and is in agreement with sediment trap d15N measurements. Estimates of the N isotope effect derived from nitrate-only d15N are higher and more variable (7.9 ± 1.5‰), consistent with an artifact from nitrate-nitrite isotope exchange. In the case of the Southern Ocean, we conclude that the d15N of nitrate + nitrite better reflects the isotope effect of nitrate assimilation. The stability of this isotope effect across the Antarctic Zone simplifies the effort to reconstruct the past degree of nitrate consumption., info:eu-repo/semantics/published

Biospektrum, 27 (4), ISSN:0947-0867

Bulk sediment δ N records from the eastern tropical Pacific (ETP) extending back to the last ice age most often show low glacial δ N, then a deglacial δ N maximum, followed by a gradual decline to a late Holocene δ N that is typically higher than that of the Last Glacial Maximum (LGM). The lower δ N of the LGM has been interpreted to reflect an ice age reduction in water column denitrification. We report foraminifera shell-bound nitrogen isotope (FB-δ N) measurements for the two species Neogloboquadrina dutertrei and Neogloboquadrina incompta over the last 35 ka in two sediment cores from the eastern equatorial Pacific (EEP), both of which have the typical LGM-to-Holocene increase in bulk sediment δ N. FB-δ N contrasts with bulk sediment δ N by not indicating a lower δ N during the LGM. Instead, the FB-δ N records are dominated by a deglacial δ N maximum, with comparable LGM and Holocene values. The lower LGM δ N of the bulk sediment records may be an artifact, possibly related to greater exogenous N inputs and/or weaker sedimentary diagenesis during the LGM. The new data raise the possibility that the previously inferred glacial reduction in ETP water column denitrification was incorrect. A review of reconstructed ice age conditions and geochemical box model output provides mechanistic support for this possibility. However, equatorial ocean circulation and nitrate-rich surface water overlying both core sites allow for other possible interpretations, calling for replication at non-equatorial ETP sites., Paleoceanography and Paleoclimatology, 36 (5), ISSN:2572-4525, ISSN:2572-4517

Rationale Since their introduction more than a decade ago, isotope ratio infrared spectroscopy (IRIS) systems have rapidly become the standard for oxygen (δ18O) and hydrogen (δ2H) isotope analysis of water samples. An important disadvantage of IRIS systems is the well-documented sample-to-sample memory effect, which requires each sample to be analyzed multiple times before the desired accuracy is reached, lengthening analysis times and driving up the costs of analyses. Methods We present an adapted set-up and calculation protocol for fully automated analysis of water samples using a Picarro L2140-i cavity ring-down spectroscopy instrument. The adaptation removes memory effects by use of a continuously moisturized nitrogen carrier gas. Water samples of 0.5 μL are measured on top of the water vapor background, after which isotope ratios are calculated by subtraction of the background from the sample peaks. Results With this new technique, single injections of water samples have internal precisions (1σ) below 0.05‰ for δ18O values and 0.1‰ for δ2H values, regardless of the isotope ratio of the previous sample. Precision is worse, however, when the isotope difference between the sample and background water is too large (i.e., exceeding approximately 9‰ for δ18O values and 70‰ for δ2H values). Isotope ratios show negligible drift across the four weeks within which the experiments were performed. The single-injection 1σ precision for 17O excess (Δ′17O) determined with this method is 60 per meg. Conclusions Our experiments demonstrate that by removing sample-to-sample memory effects with a moisturized carrier gas, the time for measurement of δ18O and δ2H values using an IRIS system can be reduced markedly without compromising the analytical precision and accuracy. Thorough replication is needed to achieve sufficiently low uncertainties for Δ′17O., Rapid Communications in Mass Spectrometry, 35 (8), ISSN:1097-0231, ISSN:0951-4198

Amphistegina are common larger benthic foraminifer in coral reefs, with a nearly circumtropical distribution, and are major contributors to the CaCO3 budget of shallow marine environments. The family Amphisteginidae is dominant in Cenozoic carbonates. However, its potential as a proxy for paleoclimate reconstruction has not been completely explored. The intratest variability in trace elements of Amphistegina lessonii has been investigated using femtosecond‐laser ablation‐inductively coupled plasma‐mass spectrometry (fs‐LA‐ICP‐MS). We collected and analyzed adult specimens of A. lessonii in September 2003, November 2003, January 2004, and March 2004, from ∼2 m water depth in the coral reefs of Akajima, Okinawa, Japan. Tests of A. lessonii from these four collections were analyzed for Mg/Ca of the septa to observe Test Size‐Lifespan relationships. The lifespan of a specimen of A. lessonii of 1,200 µm in diameter is estimated at ∼3 and ∼2 months for specimens 900 µm in size. Over the estimated lifespans, Mg/Ca of individual specimens of A. lessonii is highly variable and displays co‐variation with temperature and tidal heights. Future projects may apply and further test this approach for the reconstruction of the tropical shallow marine paleoenvironments., Geochemistry, Geophysics, Geosystems, 22 (3), ISSN:1525-2027

Summary We explored how the Younger Dryas (YD)/Holocene transition impacted tropical sea surface temperature (SST) by evaluating marine sedimentary archives at scales unattainable for conventional molecular stratigraphy. In sediments from the Cariaco Basin, we analysed the well-established UK’37 SST proxy via mass spectrometry imaging, and obtained 2D-images of sedimentary proxy distribution at 100 µm resolution and corresponding downcore SST profiles with subannual resolution. SST in the Cariaco Basin remains relatively constant over the YD/Holocene transition, suggesting a decoupling from the major environmental change associated to this event, i.e. the northward shift of the intertropical convergence zone. However, we were able to reveal a short-lived ∼50 year episode of abrupt warming during which average SST increased about 1°C. This episode is synchronous with the Preboreal Oscillation cooling, that led to drier, colder conditions in Europe and North America. The comparison of proxy values, elemental composition and sediment colour from every µm-sized spot further provides clues on SST seasonality and its modulation across the YD/Holocene transition.

The Southern Ocean is widely recognized as a potential cause of the lower atmospheric concentration of CO2 during ice ages, but the mechanism is debated. Focusing on the Southern Ocean surface, we review biogeochemical paleoproxy data and carbon cycle concepts that together favor the view that both the Antarctic and Subantarctic Zones (AZ and SAZ) of the Southern Ocean played roles in lowering ice age CO2 levels. In the SAZ, the data indicate dust-driven iron fertilization of phytoplankton growth during peak ice age conditions. In the ice age AZ, the area-normalized exchange of water between the surface and subsurface appears to have been reduced, a state that we summarize as “isolation” of the AZ surface. Under most scenarios, this change would have stemmed the leak of biologically stored CO2 that occurs in the AZ today. SAZ iron fertilization during the last ice age fits with our understanding of ocean processes as gleaned from modern field studies and experiments; indeed, this hypothesis was proposed prior to evidentiary support. In contrast, AZ surface isolation is neither intuitive nor spontaneously generated in climate model simulations of the last ice age. In a more prospective component of this review, the suggested causes for AZ surface isolation are considered in light of the subarctic North Pacific (SNP), where the paleoproxies of productivity and nutrient consumption indicate similar upper ocean biogeochemical changes over glacial cycles, although with different timings at deglaciation. Among the proposed initiators of glacial AZ surface isolation, a single mechanism is sought that can explain the changes in both the AZ and the SNP. The analysis favors a weakening and/or equatorward shift in the upwelling associated with the westerly winds, occurring in both hemispheres. This view is controversial, especially for the SNP, where there is evidence of enhanced upper water column ventilation during the last ice age. We offer an interpretation that may explain key aspects of the AZ and SNP observations. In both regions, with a weakening in westerly wind-driven upwelling, nutrients may have been “mined out” of the upper water column, possibly accompanied by a poleward “slumping” of isopycnals. In the AZ, this would have encouraged declines in both the nutrient content and the formation rate of new deep water, each of which would have contributed to the lowering of atmospheric CO2. Through several effects, the reduction in AZ upwelling may have invigorated the upwelling of deep water into the low latitude pycnocline, roughly maintaining the pycnocline’s supply of water and nutrients so as to (1) support the high productivity of the glacial SAZ and (2) balance the removal of water from the pycnocline by the formation of Glacial North Atlantic Intermediate Water. The proposed return route from the deep ocean to the surface resembles that of Broecker’s (1991) “global ocean conveyor,” but applying to the ice age as opposed to the modern ocean., Quaternary Science Reviews, 254, ISSN:0277-3791

Previous studies have suggested that during the late Pleistocene ice ages, surface-deep exchange was somehow weakened in the Southern Ocean’s Antarctic Zone, which reduced the leakage of deeply sequestered carbon dioxide and thus contributed to the lower atmospheric carbon dioxide levels of the ice ages. Here, high-resolution diatom-bound nitrogen isotope measurements from the Indian sector of the Antarctic Zone reveal three modes of change in Southern Westerly Wind–driven upwelling, each affecting atmospheric carbon dioxide. Two modes, related to global climate and the bipolar seesaw, have been proposed previously. The third mode—which arises from the meridional temperature gradient as affected by Earth’s obliquity (axial tilt)—can explain the lag of atmospheric carbon dioxide behind climate during glacial inception and deglaciation. This obliquity-induced lag, in turn, makes carbon dioxide a delayed climate amplifier in the late Pleistocene glacial cycles., info:eu-repo/semantics/published

© 2020 The Authors. Rapid Communications in Mass Spectrometry published by John Wiley & Sons Ltd Rationale: Oxygen (δ18O) and carbon (δ13C) isotope analysis of foraminifera and other CaCO3 samples has been a key technique for paleoceanographical and paleoclimatological research for more than 60 years. There is ongoing demand for the analysis of ever smaller CaCO3 samples, driven, for example, by the desire to analyse single specimen planktic foraminifera, or small samples of tooth enamel. Methods: We present a continuous-flow mass spectrometric technique that uses cryo-focusing of sample CO2 to analyse CaCO3 samples in a weight range between 10 and 3 μg. These are considerably lower sample weights than achievable on most currently available standard instrumentation. The technique is automated, so that sample throughput lies at >60 samples per day. The method involves an on-line vial-flushing routine designed to remove machine drift due to blank CO2 build-up in the sample vials. Results: In a series of experiments the effect of blank CO2 build-up is quantified, and outgassing from the chlorobutyl septa identified as the source. An improved flushing routine together with the use of a cryo-focusing step in the analysis is demonstrated to provide the analytical stability and sensitivity to analyse CaCO3 samples in a weight range between 10 and 3 μg at ≤0.1‰ precision (1σ) for both δ18O and δ13C values. The technique yields similarly precise results for the analysis of the structural carbonate fraction of small tooth enamel samples. Conclusions: This study demonstrates that high-precision oxygen and carbon isotope analysis is possible on CaCO3 samples smaller than 5 μg by use of a continuous-flow isotope technique. Of key importance are (1) the application of a cold trap that drastically reduces sample gas loss, and (2) a modified flushing regime that eliminates increasing background CO2 build-up in sample vials during longer automated sample runs., Rapid Communications in Mass Spectrometry, 34 (19), ISSN:1097-0231, ISSN:0951-4198

The role of aerosolized SARS-CoV-2 viruses in airborne transmission of COVID-19 is debated. The transmitting aerosol particles are generated through the breathing and vocalization by infectious subjects. Some authors state that this represents the dominant route of spreading, while others dismiss the option. Public health organizations generally categorize it as a secondary transmission pathway. Here we present a simple, easy-to-use spreadsheet algorithm to estimate the infection risk for different indoor environments, constrained by published data on human aerosol emissions, SARS-CoV-2 viral loads, infective dose and other parameters. We evaluate typical indoor settings such as an office, a classroom, a choir practice room and reception/party environments. These are examples, and the reader is invited to use the algorithm for alternative situations and assumptions. Our results suggest that aerosols from highly infective subjects can effectively transmit COVID-19 in indoor environments. This “highly infective” category represents about one fifth of the patients tested positive for SARS-CoV-2. We find that “super infective” subjects, representing the top few percent of positive-tested ones, plus an unknown fraction of less, but still highly infective, high aerosol-emitting subjects, may cause COVID-19 clusters (>10 infections), e.g. in classrooms, during choir singing and at receptions. The highly infective ones also risk causing such events at parties, for example. In general, active room ventilation and the ubiquitous wearing of face masks (i.e. by all subjects) may reduce the individual infection risk by a factor of five to ten, similar to high-volume HEPA air filtering. The most effective mitigation measure studied is the use of high-quality masks, which can drastically reduce the indoor infection risk through aerosols.

We investigated rock varnish, a thin, manganese- and iron-rich, dark surface crust, on basaltic lava flows and petroglyphs in the Owens and Rose Valleys (California) by portable X-ray fluorescence (pXRF) and femtosecond laser-ablation inductively-coupled-plasma mass spectrometry (fs-LA-ICPMS). The major element composition of the varnish was consistent with a mixture of Mn-Fe oxyhydroxides and clay minerals. As expected, it contained elevated concentrations of elements that are typically enriched in rock varnish, e.g., Mn, Pb, Ba, Ce, and Co, but also showed unusually high enrichments in U, Cu, and Th. The rare earth and yttrium (REY) enrichment pattern revealed a very strong positive cerium (Ce) anomaly and distinct negative europium (Eu) and Y anomalies. The light rare earth elements (REE) were much more strongly enriched than the heavy REY. These enrichment patterns are consistent with a formation mechanism by leaching of Mn and trace elements from aeolian dust, reprecipitation of Mn and Fe as oxyhydroxides, and scavenging of trace elements by these oxyhydroxides. We inferred accumulation rates of Mn and Fe in the varnish from their areal densities measured by pXRF and the known ages of some of the lava flow surfaces. The areal densities of Mn and Fe, as well as their accumulation rates, were comparable to our previous results from the desert of Saudi Arabia. There was a moderate dependence of the Mn areal density on the inclination of the rock surfaces, but no relationship to its cardinal orientation. We attempted to use the degree of varnish regrowth on the rock art surfaces as an estimate of their age. While an absolute dating of the petroglyphs was not possible because of the lack of suitable calibration surfaces and a considerable amount of variability, the measured degree of varnish regrowth on the various petroglyphs was consistent with chronologies based on archeological and other archaeometric techniques. In particular, our results suggest that rock art creation in the study area continued over an extended period of time, possibly starting around the Pleistocene/Holocene transition and extending into the last few centuries., PLoS ONE, 15 (8), ISSN:1932-6203